Indium arsenide nanocrystals and methods of making the same

ABSTRACT

The present invention provides high quality monodisperse or substantially monodisperse InAs nanocrystals in the as-prepared state. In some embodiments, the as-prepared substantially monodisperse InAs nanocrystals demonstrate a photoluminescence of between about 700 nm and 1400 nm.

RELATED APPLICATIONS

The present application claims priority pursuant to 35 U.S.C. §119(e) toU.S. Provisional Patent Application Ser. No. 61/060,463, filed Jun. 10,2008, which is incorporated herein by reference in its entirety.

STATEMENT OF GOVERNMENT LICENSE RIGHTS

The present invention was made through the support of the NationalInstitute of Health (NIH) (Grant Numbers 2R44GM06065-03 REVISED and5R43EB005072-02). The United States Government has certain licenserights in this invention.

FIELD OF THE INVENTION

The present invention relates to nanocrystalline materials and, inparticular, to nanocrystalline semiconductor materials and methods ofmaking and using the same.

BACKGROUND OF THE INVENTION

Colloidal semiconductor nanocrystals or quantum dots have generatedsignificant interest for their promise in developing advanced opticalmaterials. Size-dependent emission is attractive property ofsemiconductor nanocrystals allowing their use in a variety of wavelengthdependent applications.

Biological labeling, for example, is expected to be a significantapplication of semiconductor nanocrystals. Particularly,photoluminescent (PL) quantum dots having emission in the near-infrared(NIR) region of the electromagnetic spectrum (700-1400 nm) are likelyout-perform other available biological labels for in-vivo imagingbecause of their large absorption cross section and narrow emissionbands. Moreover, semiconductor nanocrystals can also find significantapplication in display technologies, thermoelectrics, telecommunicationsand signaling, photonics and photovoltaic apparatus.

Nevertheless, the synthetic chemistry of semiconductor nanocrystals,including NIR emitting nanocrystals, is challenging and has inspiredcontinuous efforts for developing high performance nanocrystals for usein various applications. Generally speaking, current limitations ofthese materials include low emission efficiency, broad spectrum width,poor color control and/or poor stability.

SUMMARY

In view of the foregoing limitations, the present invention providesmonodisperse or substantially monodisperse indium arsenide (InAs)nanocrystals in the as-prepared state. In being monodisperse orsubstantially monodisperse, InAs nanocrystals of the present inventiondemonstrate a narrow size distribution. The narrow size distributioncharacterizing the monodispersity or substantial monodispersity of theInAs nanocrystals is evidenced by the photoluminescence emission line ofthe nanocrystals which, in some embodiments, has a full width at halfmaximum (FWHM) of about 55-85 nm. In other embodiments, thephotoluminescence emission line of the InAs nanocrystals has a FWHM orabout 60-70 nm. In another embodiment, the photoluminescence emissionline of the InAs nanocrystals has a FWHM of about 55-65 nm.

In some embodiments, the as-prepared InAs nanocrystals demonstrate aphotoluminescence of between about 700 nm and 1400 nm or between about800 nm and 1100 nm.

The as-prepared state of the InAs nanocrystals described herein, in someembodiments, precludes the need for additional processing steps,including size sorting to produce a monodisperse or substantiallymonodisperse composition.

In some embodiments, as-prepared InAs nanocrystals have a size less thanabout 5 nm. In other embodiments, InAs nanocrystals have a size lessthan about 3 nm or less than about 2 nm. In a further embodiment InAsnanocrystals have a size ranging from about 1 nm to about 3 nm.

In another aspect, as-prepared monodisperse or substantiallymonodisperse nanocrystals having a core/shell construction are provided.Embodiments of monodisperse or substantially monodisperse core/shellnanocrystals described herein comprise an InAs core and at least oneshell, the at least one shell comprising a II/VI compound or a III/Vcompound. In some embodiments, the III/V compound is different fromInAs. Groups II, III, V, and VI, as used herein, refer to Groups IIB,IIIA, VA, and VIA of the periodic table according to the American CASdesignation. For example Group IIB corresponds to the zinc family, GroupIIIA corresponds to the boron family, Group VA corresponds to thenitrogen family, and Group VIA corresponds to the chalcogens.

In some embodiments, a shell comprises one monolayer of a II/VI or aIII/V compound. In other embodiments, a shell comprises a plurality ofmonolayers of a II/VI or a III/V compound. A shell, according to someembodiments, can comprise any desired number of monolayers of a II/VI ora III/V compound.

Moreover, in some embodiments, core/shell nanocrystals comprise an InAscore and a plurality of shells. In one embodiment, for example, acore/shell nanocrystal comprises an InAs core, a first shell and asecond shell, wherein the first and second shells each comprise one ormore monolayers of a II/VI compound or a III/V compound. In someembodiments, the compositions of individual shells are chosenindependently of one another.

In some embodiments, the bandgap of a shell material is larger than thebandgap of the InAs core. In some embodiments, the bandgap of a shellmaterial is larger than the bandgap of the InAs core and any otherintervening shell material(s). In one embodiment, for example, acore/shell nanocrystal comprises an InAs core, a first shell and asecond shell, wherein the first shell has a larger bandgap than the coreand the second shell has a larger bandgap than the first shell.Alternatively, in some embodiments, the bandgap of a shell material issmaller than the bandgap of the InAs core.

In some embodiments, as-prepared InAs core/shell nanocrystals display aphotoluminescence emission line having a FWHM of about 55-85 nm. Inother embodiments, InAs core/shell nanocrystals display aphotoluminescence emission line having a FWHM of about 60-75 nm. Inanother embodiment, InAs core/shell nanocrystals display aphotoluminescence emission line having a FWHM of about 55-65 nm. In someembodiments, core/shell nanocrystals described herein have aphotoluminescence ranging from about 700 nm to about 1400 nm or fromabout 800 nm to about 1100 nm.

Core/shell semiconductor nanocrystals, in which the core compositiondiffers from the composition of the shell that surrounds the core, areuseful for many optical applications. If the band offsets of thecore/shell structures are type-I, and the shell semiconductor possessesa larger bandgap than the core material, the photo-generated electronand hole inside a nanocrystal will be mostly confined within the core.As used herein, type-I band offsets refer to a core/shell electronicstructure wherein both conduction and valence bands of the shellsemiconductor are simultaneously either higher or lower than those ofthe core semiconductor. Consequently, conventional core/shellnanocrystals can show high photoluminescence (PL) andelectroluminescence efficiencies and can be more stable againstphoto-oxidation than “plain core” semiconductor nanocrystals comprisinga single material, provided that the bandgap of the core semiconductoris smaller than that of the shell semiconductor.

In some embodiments, monodisperse or substantially monodisperse InAscore/shell nanocrystals described herein display a photoluminescentquantum yield (PL QY) of up to about 90%. In other embodiments, InAscore/shell nanocrystals have a PL QY up to about 80% or up to about 60%.In some embodiments, core/shell nanocrystals have a PL QY greater than70% or greater than 75%. In another embodiment, InAs core/shellnanocrystals have a PL QY ranging from about 40% to about 90%. In afurther embodiment, InAs core/shell nanocrystals have a PL QY greaterthan 90% or less than 40%.

In some embodiments, InAs nanocrystals described herein, including InAsnanocrystals having a core/shell construction, further comprise one or aplurality of ligands associated with a surface of the nanocrystals.Ligands, in some embodiments, can change the solubility and/ordispersability of InAs nanocrystals in various polar and/or non-polarmedia.

In one embodiment, ligands comprise hydrophobic chemical species. Inanother embodiment, ligands comprise hydrophilic chemical species.Ligands can be associated with nanocrystal surfaces through covalentbonds, electrostatic interactions, van der Waals interactions,dipole-dipole interactions, hydrophobic interactions or combinationsthereof. In some embodiments, ligands comprise dendritic ligands.

In another aspect, a composition comprising an aqueous solution of InAsnanocrystals described herein is provided. In one embodiment, forexample, an aqueous solution comprises a plurality of any of thecore/shell nanocrystals described herein. In some embodiments,nanocystals of an aqueous solution have a hydrodynamic size less thanabout 10 nm. In some embodiments, nanocrystals of an aqueous solutionhave a hydrodynamic size up to about 9 nm. The hydrodynamic size of thenanocrystals, in some embodiments, includes any size contributed by oneor more ligands associated with a surface of the nanocrystal.

Additionally, in some embodiments, nanocrystals described herein, in anaqueous solution, have a PL QY greater than about 30%. In anotherembodiment, nanocrystals in an aqueous solution have a PL QY greaterthan about 40%. In some embodiments, nanocrystals in an aqueous solutionhave a PL QY greater than about 50% or greater than about 60%.

In some embodiments, a composition comprising an aqueous solution of anyof the nanocrystals described herein is a biological labelingcomposition. In some embodiments, a biological labeling composition canbe used to identify certain tissues or other biological structures of anorganism. Organisms can include single cellular organism ormulti-cellular organisms, including mammals.

In another aspect, methods of synthesizing as-prepared monodisperse orsubstantially monodisperse InAs nanocrystals are provided. In oneembodiment a method of synthesizing monodisperse or substantiallymonodisperse InAs nanocrystals comprises combining an indium (In)precursor, a ligand, and a solvent to form an In-ligand complex,admixing an arsenic (As) precursor with the In-ligand complex at a firsttemperature sufficient to form InAs nanocrystals, and heating the InAsnanocrystals to a second temperature to provide monodisperse orsubstantially monodisperse InAs nanocrystals. The second temperature,according to some embodiments, is greater than the first temperature.Additionally, in some embodiments, the solvent comprises anon-coordinating solvent.

In methods of synthesizing monodisperse or substantially monodisperseInAs nanocrystals described herein, the InAs nanocrystals have a firstconcentration at the first temperature, and the monodisperse orsubstantially monodisperse InAs nanocrystals have a second concentrationat the second temperature, wherein the second concentration is less thanthe first concentration. In some embodiments, the second concentrationis substantially less than the first concentration. Moreover, the InAsnanocrystals have a first average size at the first temperature, and themonodisperse or substantially monodisperse InAs nanocrystals have asecond average size at the second temperature wherein the second averagesize is greater than the first average size.

In another embodiment, a method of synthesizing monodisperse orsubstantially monodisperse InAs nanocrystals further comprises forming afirst shell comprising a material M¹X¹ on at least one of themonodisperse or substantially monodisperse InAs nanocrystals, wherein M¹is a cation and X¹ is an anion. In some embodiments, forming a firstshell comprises forming at least one monolayer of a first shell materialM¹X¹ by contacting the substantially monodisperse InAs nanocrystals, inan alternating manner, with a cation (M¹) precursor solution in anamount effective to form a monolayer of the cation, and an anion (X¹)precursor solution in an amount effective to form a monolayer of theanion, wherein M¹X¹ comprises a stable, nanometer sized inorganic solidand wherein M¹X¹ is selected from a II/V compound or a III/V compound.In some embodiments, a UV compound is different from InAs. Anyadditional number of monolayers of the first shell material M¹X¹ can beformed according to the foregoing procedure. In some embodiments, afirst shell comprises up to 15 monolayers of M¹X¹.

In some embodiments, the monodisperse or substantially monodisperse InAsnanocrystals are contacted first with the cation precursor solution toprovide InAs nanocrystals with a monolayer of cation. In otherembodiments, the monodisperse or substantially monodisperse InAsnanocrystals are contacted first with the anion precursor solution toprovide the nanocrystals with a monolayer of anion. In some embodiments,the addition of cation precursor solution and anion precursor solutionto a solution of InAs nanocrystals in an alternating manner results in asolution comprising InAs nanocrystals comprising a first shell, thesolution also comprising cation precursor solution and anion precursorsolution.

In some embodiments, by adding cation precursor and anion precursor inan alternating manner to the reaction vessel comprising InAsnanocrystals, the InAs nanocrystals are not washed or otherwise purifiedbetween the alternating additions of cation and anion precursorsolutions.

Moreover, in some embodiments, a method of synthesizing monodisperse orsubstantially monodisperse InAs nanocrystals further comprises formingsubsequent or additional shells comprising a material M²X². Subsequentshells or additional shells can be formed in the same or substantiallythe same manner as the formation of the first shell. In one embodiment,forming at least one monolayer of additional shell material M²X²comprises contacting the substantially monodisperse InAs nanocrystalshaving a first shell, in an alternating manner, with a cation (M²)precursor solution in an amount effective to form a monolayer of thecation, and an anion (X²) precursor solution in an amount effective toform a monolayer of the anion, wherein M²X² comprises a stable,nanometer sized inorganic solid and wherein M²X² is selected from a II/Vcompound or a III/V compound. In some embodiments, a III/V compound isdifferent than InAs.

In some embodiments, the first shell and any subsequent shells areconstructed independently and without reference to one another. As aresult, in one embodiment, the first shell and any subsequent shells cancomprise the same material. In another embodiment, the first shell andany subsequent shells can comprise different materials.

The foregoing methods provide a “one-pot” synthesis of monodisperse orsubstantially monodisperse as-prepared InAs nanocrystals, including InAsnanocrystals demonstrating core/shell architectures, includingcore/multiple shell architectures.

In a further aspect, a method of determining the core size ofnanocrystals having a core/shell architecture is provided. In oneembodiment, a method for determining the core size of a core/shellnanocrystal comprises determining the size of the core/shellnanocrystal, the core comprising a material M¹X¹ and the shellcomprising a material M²X², wherein M¹ and M² are cations and X¹ and X²are anions, determining the ratio of M¹ to M², and correlating the ratioof M¹ to M² to the volume of the core of the nanocrystal. In someembodiments, the ratio of M¹ to M² can be correlated to the volume ofthe core by providing a spherical model.

These and other embodiments are described in further detail in thedetailed description which follows.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 illustrates the first exciton absorption peak for InAsnanocrystals according to some embodiments of the present invention.

FIG. 2 illustrates the PL QY of monodisperse or substantiallymonodisperse InAs core/shell nanocrystals according to one embodiment ofthe present invention.

FIG. 3 illustrates an InAs core/shell nanocrystal having a plurality ofligands associated with a surface of the nanocrystal according to oneembodiment of the present invention.

FIG. 4 illustrates the hydrodynamic size of InAs core/shell nanocrystalsaccording to some embodiments of the present invention.

FIG. 5 illustrates the temporal evolution of InAs particle size and InAsparticle concentration according to one embodiment of a method ofsynthesizing monodisperse or substantially monodisperse InAsnanocrystals of the present invention.

FIG. 6 illustrates absorption spectra of InAs nanocrystals according toone embodiment of a method of synthesizing monodisperse or substantiallymonodisperse InAs nanocrystals of the present invention.

FIG. 7 illustrates as-prepared monodisperse or substantiallymonodisperse InAs nanocrystals according to one embodiment of thepresent invention.

DETAILED DESCRIPTION

The present invention provides monodisperse or substantiallymonodisperse InAs nanocrystals in the as-prepared state. In beingmonodisperse or substantially monodisperse, the InAs nanocrystalsdemonstrate a narrow size distribution. The narrow size distributioncharacterizing the monodispersity or substantial monodispersity of theInAs nanocrystals is evidenced by the photoluminescence emission line ofthe nanocrystals which, in some embodiments, has a FWHM of about 55-85nm, of about 60-70 nm or of about 55-65 nm. In some embodiments, theas-prepared InAs nanocrystals demonstrate a photoluminescence of betweenabout 700 nm and 1400 nm or between about 800 nm and 1100 nm.

The as-prepared state of the InAs nanocrystals, in some embodiments,precludes the need for additional processing steps including sizesorting to produce a monodisperse or substantially monodispersecomposition.

In some embodiments, as-prepared InAs nanocrystals have a size less thanabout 5 nm. In other embodiments, InAs nanocrystals have a size lessthan about 3 nm or less than about 2 nm. In a further embodiment InAsnanocrystals have a size ranging from about 1 nm to about 3 nm. Inanother embodiment, as-prepared InAs nanocrystals have a size less thanabout 1 nm or greater than about 5 nm.

In another aspect, monodisperse or substantially monodispersenanocrystals having a core/shell construction are provided. Embodimentsmonodisperse or substantially monodisperse as-prepared nanocrystalshaving a cores/shell construction comprise an InAs core and at least oneshell, the at least one shell comprising a II/VI compound or a III/Vcompound. In some embodiments, the III/V compound is different fromInAs. In one embodiment, for example, monodisperse or substantiallymonodisperse InAs core/shell nanocrystals comprise InAs/InP, InAs/ZnSeand InAs/ZnS.

In some embodiments, monodisperse or substantially monodispersecore/shell nanocrystals comprise an InAs core and a plurality of shells.In one embodiment, for example, nanocrystals comprise a core/shell/shellarchitecture having an InAs core, a first shell and a second shell,wherein the first and second shells each comprise a II/VI compound or aMN compound. In some embodiments, the compositions of individual shellsare chosen independently of one another. In some embodiments, forexample, nanocrystals having a core/shell/shell structure compriseInAs/InP/ZnSe. In other embodiments, nanocrystals having acore/shell/shell structure comprise InAs/InP/ZnS. In some embodiments,InAs nanocrystals comprise a core/shell/shell/shell structure includingbut not limited to InAs/InP/ZnSe/ZnSe, InAs/InP/ZnSe/ZnS,InAs/InP/ZnS/ZnS or InAs/InP/ZnS/ZnSe.

A shell of a core/shell nanocrystal described herein, in someembodiments, comprises one monolayer of a II/VI or a III/V compound. Inother embodiments, a shell comprises a plurality of monolayers of aII/VI or a III/V compound. A shell, according to some embodiments, cancomprise any desired number of monolayers of a II/VI or a III/Vcompound. In some embodiments, a shell of a core/shell nanocrystalcomprises 1 to 15 monolayers of a II/VI or a III/V compound. In someembodiments a shell of a core/shell nanocrystal comprises 2-5 monolayersof a II/VI or a III/V compound.

In some embodiments, the bandgap of a shell material is larger than thebandgap of the InAs core. In some embodiments, the bandgap of a shellmaterial is larger than the bandgap of the InAs core and any otherintervening shell material(s). In one embodiment, for example, acore/shell nanocrystal comprises an InAs core, a first shell and asecond shell, wherein the first shell has a larger bandgap than the coreand the second shell has a larger bandgap than the first shell.Alternatively, in some embodiments, the bandgap of a shell material issmaller than the bandgap of the InAs core.

In some embodiments, InAs core/shell nanocrystals display aphotoluminescence emission peak having a FWHM of about 55-85 nm, ofabout 60-70 nm or of about 55-65 nm. In some embodiments, core/shellnanocrystals described herein have a photoluminescence ranging fromabout 700 nm to about 1400 nm or from about 800 nm to about 1100 nm.

In some embodiments, as-prepared monodisperse or substantiallymonodisperse InAs core/shell nanocrystals described herein display aphotoluminescent quantum yield (PL QY) of up to about 90%. In otherembodiments, InAs core/shell nanocrystals have a PL QY up to about 80%or up to about 60%. In some embodiments, InAs core/shell nanocrystalshave a PL QY greater than 70% or greater than 75%. In anotherembodiment, InAs core/shell nanocrystals have a PL QY ranging from about40% to about 90%. In a further embodiment, InAs core/shell nanocrystalshave a PL QY greater than 90% or less than 40%.

FIG. 1 illustrates the first exciton absorption peak for InAsnanocrystals according to some embodiments of the present invention. Asprovided in FIG. 1, as-prepared monodisperse or substantiallymonodisperse InAs nanocrystals can display a first exciton absorptionpeak ranging from about 550 nm to about 1050 nm thereby providing avariety of absorption and photoluminescence options for an assortment ofapplications such as biological labeling, signaling and sensing.

FIG. 2 illustrates the PL QY of as-prepared monodisperse orsubstantially monodisperse InAs nanocrystals according to one embodimentof the present invention. In the embodiment illustrated in FIG. 2, theas-prepared nanocrystals comprised a core/shell architecture having anInAs core followed by an InP first shell and a ZnSe second shell(InAs/InP/ZnSe). The as prepared core/shell nanocrystals demonstrated aPL QY of about 76%, the photoluminescence emission line having a FWHM ofabout 60-75 nm.

In some embodiments, InAs nanocrystals described herein, including InAsnanocrystals having a core/shell construction, further comprise one or aplurality of ligands associated with a surface of the nanocrystals.Ligands, in some embodiments, can change the solubility and/ordispersability of the InAs nanocrystals in various polar and/ornon-polar media.

In some embodiments, ligands for association with nanocrystal surfacesare chosen according to the polarity of the medium in which thenanocrystals are to be disposed. Ligands comprising one or more polar orhydrophilic functionalities, for example, can be chosen in embodimentswherein nanocrystals describe herein are disposed in polar or aqueousmedia. In some embodiments, ligands having hydrophobic functionalitiescan be chosen wherein nanocrystals are disposed in non-polar media.

Ligands can be associated with nanocrystal surfaces through covalentbonds, electrostatic interactions, van der Waals interactions,dipole-dipole interactions, hydrophobic interactions or combinationsthereof. In some embodiments, ligands comprise dendritic ligands such asthose described U.S. Pat. No. 7,153,703, which is hereby incorporated byreference in its entirety.

FIG. 3 illustrates an as-prepared core/shell nanocrystal having aplurality of ligands associated with a surface of the nanocrystalaccording to one embodiment of the present invention. In the embodimentillustrated in FIG. 3, hydrophobic ligands associated with anas-prepared InAs/InP/ZnSe core/shell nanocrystal are substituted byhydrophilic mercaptopropionic acid ligands, thereby facilitating placingthe nanocrystal in polar or aqueous media.

InAs nanocrystals, including InAs nanocrystals having a core/shellarchitectures, in some embodiments, are stable in polar or non-polarsolvents. In one embodiment, InAs nanocrystals display a hydrodynamicsize less than about 10 nm. In some embodiments, InAs nanocrystals havea hydrodynamic size less than about 8 nm, less than about 7 nm or lessthan about 6 nm. In a further embodiment, InAs nanocrystals have ahydrodynamic size less than about 5 nm or a hydrodynamic size rangingfrom about 3 nm to about 9 nm. The hydrodynamic size of a nanocrystal,in some embodiments, includes any size contributed by one or moreligands associated with a surface of the nanocrystal. FIG. 4, forexample, illustrates the hydrodynamic size distribution of core/shellnanocrystals described herein having the construction InAs/InP/ZnSe. Asillustrated in FIG. 4, the InAs/InP/ZnSe nanocrystals demonstrated ahydrodynamic size less than or equal to 10 nm.

Additionally, in some embodiments, nanocrystals described herein, in anaqueous solution, have a PL QY greater than about 30%. In anotherembodiment, nanocrystals in an aqueous solution have a PL QY greaterthan about 40%. In some embodiments, nanocrystals in an aqueous solutionhave a PL QY greater than about 50% or greater than about 60%.

In some embodiments, a composition comprising an aqueous solution of anyof the nanocrystals described herein is a biological labelingcomposition. In some embodiments, a biological labeling composition canbe used to identify certain tissues or other biological structures of anorganism. Organisms can include single cellular organism ormulti-cellular organisms, including mammals.

In another aspect, methods of synthesizing as-prepared monodisperse orsubstantially monodisperse InAs nanocrystals are provided. In oneembodiment a method of synthesizing monodisperse or substantiallymonodisperse InAs nanocrystals comprises combining an In precursor, aligand, and a solvent to form an In-ligand complex, admixing an Asprecursor with the In-ligand complex at a first temperature sufficientto form InAs nanocrystals, and heating the InAs nanocrystals to a secondtemperature to provide monodisperse or substantially monodisperse InAsnanocrystals. The second temperature, according to some embodiments, isgreater than the first temperature.

In some embodiments, an indium precursor comprises a indium oxide, anindium carbonate, an indium bicarbonate, an indium sulfate, an indiumsulfite, an indium phosphate, an indium phosphite, an indium halide, anindium carboxylate, an indium acetate, an indium hydroxide, an indiumalkoxide, an indium thiolate, an indium amide, an indium imide, anindium alkyl, an indium aryl, an indium coordination complex, an indiumsolvate, an indium salt, or a mixture thereof.

Moreover, a ligand suitable for use in methods described herein, in someembodiments, comprises a fatty acid, a fatty amine, a phosphine, aphosphine oxide, a phosphonic acid, a phosphinic acid, a sulphonic acid,or any combination thereof. In some embodiments, a ligand comprises upto about 30 carbon atoms. In another embodiment, a ligand comprises upto about 45 carbon atoms.

In some embodiments, the solvent in which the In precursor and ligandare disposed is a coordinating solvent. In other embodiments, thesolvent in which the In precursor and the ligand are disposed is anon-coordinating solvent. In one embodiment, a suitable non-coordinatingsolvent comprises octadecene (ODE). Additional suitable non-coordinatingsolvents can be generally selected using the following guidelines.Suitable non-coordinating solvents, in some embodiments, should have amelting point less than about 25° C. and a boiling point greater thanabout 250° C. Moreover, reactants and products alike, in someembodiments, should be soluble and stable in the selected solvent.

As provided herein, the As precursor is added to the cation precursor,ligand, and solvent at a first temperature to form InAs nanocrystals. Insome embodiments, the first temperature ranges from about 100° C. toabout 200° C. In other embodiments, the first temperature ranges fromabout 120° C. to about 150° C. In a further embodiment, the firsttemperature ranges from about 50° C. to about 100° C. The formed InAsnanocrystals display a first average size at the first temperature.

Subsequent to formation, the InAs nanocrystals are heated to a secondtemperature to provide monodisperse or substantially monodisperse InAsnanocrystals. The second temperature, according to some embodiments, isgreater than the first temperature. In some embodiments, the secondtemperature ranges from about 120° C. to about 300° C. In otherembodiments, the second temperature ranges from about 150° C. to about270° C. or from about 200° C. to about 250° C. In some embodiments, thesecond temperature is less than about 120° C. or greater than about 300°C.

While not wishing to be bound by any theory, it is believed that heatingthe InAs nanocrystals formed at the first temperature to the secondtemperature results in a self-focusing of the size distribution of theInAs nanocrystals to produce monodisperse or substantially monodisperseInAs nanocrystals. During self-focusing of the size distribution, it isbelieved that the initial InAs nanoparticle concentration decreasessubstantially in the growth process as monomers are driven from smallInAs nanocrystals to relatively large nanocrystals via inter-particlediffusion resulting from solubility gradients between the closely packedInAs nanocrystals. In some embodiments, the InAs nanoparticleconcentration decreased by more than an order of magnitude. Drivingmonomers from the small InAs nanocrystals to the larger InAsnanocrystals provides a reduction in particle concentration as smallerInAs nanocrystals are dissolved or otherwise extinguished.

The “self-focusing” nature of the growth of the InAs nanocrystals wasverified by quantitative analysis. FIG. 5 illustrates the temporalevolution of average InAs nanocrystal size (left) and InAs nanocrystalconcentration (right) for monodisperse or substantially monodisperseInAs nanocrystals produced in accordance with methods described herein.Upon the rapid growth of the InAs nanocrystals (FIG. 5, left), the InAsnanocrystal concentration decreased sharply (FIG. 5, right). Forexample, when the InAs nanocrystals were heated to a temperature of 300°C., the initial particle concentration was 6.6×10⁻⁴ (mol/L) and thefinal particle concentration decreased by 30 times from this initialvalue (FIG. 5, right bottom), which is equivalent to 97% of the initialInAs nanoparticles being completely dissolved. These results areconsistent with the features of self-focusing of size distribution.Moreover, the narrow FWHM values of photoluminescence emission lines forInAs nanocrystals provided herein are consistent with the substantiallymonodisperse size distribution.

FIG. 6 additionally demonstrates self-focusing of the size distributionof InAs nanocrystals at several temperatures according to someembodiments of the present invention. As illustrated at each of thetemperatures (T_(sf)) of FIG. 6, small InAs nanocrystals are initiallypresent as evidenced by the absorption peaks at 420 nm and 460 nm. Astime progresses to 75 minutes, the absorption peaks at 420 nm and 460nm, associated with the small InAs nanocrystals, diminish as a singleabsorption peak grows indicating the production of larger, substantiallymonodisperse InAs nanocrystals.

In another embodiment, a method of synthesizing monodisperse orsubstantially monodisperse InAs nanocrystals further comprises formingone or a plurality of shells on the InAs core nanocrystals. In someembodiments, one or a plurality of shells can be formed on InAs corenanocrystals according to successive ion layer absorption and reaction(SILAR) techniques.

In one embodiment, a method of synthesizing monodisperse orsubstantially monodisperse InAs nanocrystals further comprises forming afirst shell comprising a material M¹X¹ on at least one of themonodisperse or substantially monodisperse InAs nanocrystals, wherein M¹is a cation and X¹ is an anion. In some embodiments, forming a firstshell material on at least one of the substantially monodispersenanocrystals comprises forming at least one monolayer of a first shellmaterial M¹X¹ by contacting the substantially monodisperse InAsnanocrystals, in an alternating manner, with a cation (M¹) precursorsolution in an amount effective to form a monolayer of the cation, andan anion (X¹) precursor solution in an amount effective to form amonolayer of the anion, wherein M¹X¹ comprises a stable, nanometer sizedinorganic solid and wherein M¹X¹ is selected from a II/V compound or aIII/V compound. In some embodiments, a III/V compound is different fromInAs. Any additional number of monolayers of the first shell materialM¹X¹ can be formed according to the foregoing procedure. In someembodiments, a first shell comprises up to 15 monolayers of M¹X¹.

In some embodiments, the monodisperse or substantially monodisperse InAsnanocrystals are contacted first with the cation precursor solution toprovide InAs nanocrystals with a monolayer of cation. In otherembodiments, the monodisperse or substantially monodisperse InAsnanocrystals are contacted first with the anion precursor solution toprovide the nanocrystals with a monolayer of anion. In some embodiments,the addition of cation precursor solution and anion precursor solutionto a solution of InAs nanocrystals in an alternating manner results in asolution comprising InAs nanocrystals comprising a first shell, thesolution also comprising cation precursor solution and anion precursorsolution.

In some embodiments, by adding cation precursor and anion precursor inan alternative manner to the reaction vessel comprising InAsnanocrystals, the InAs nanocrystals are not washed or otherwise purifiedbetween the alternating additions of cation and anion precursorsolutions.

Moreover, in some embodiments, a method of synthesizing monodisperse orsubstantially monodisperse InAs nanocrystals further comprises formingsubsequent or additional shells comprising a material M²X². Subsequentshells or additional shells can be formed in the same or substantiallythe same manner as the formation of the first shell. In one embodiment,comprises forming at least one monolayer of additional shell materialM²X² by contacting the substantially monodisperse InAs nanocrystalshaving a first shell, in an alternating manner, with a cation (M²)precursor solution in an amount effective to form a monolayer of thecation, and an anion (X²) precursor solution in an amount effective toform a monolayer of the anion, wherein M²X² comprises a stable,nanometer sized inorganic solid and wherein M²X² is selected from a II/Vcompound or a III/V compound different from InAs.

In some embodiments, the first shell and any subsequent shells areconstructed independently and without reference to one another. As aresult, in one embodiment, the first shell and any subsequent shells cancomprise the same material. In another embodiment, the first shell andany subsequent shells can comprise different materials.

Moreover, in some embodiments, an amount of cation and anion precursoreffective to form a monolayers of cation and anion on nanocrystals canbe determined by calculating the number of surface atoms of a givensized core/shell nanocrystal.

Shells can be grown on InAs cores at a variety of temperatures. In someembodiments, the temperature of shell growth is dependent upon thematerials used to form the shell. In some embodiments, shells are grownat a temperature ranging from about 180° C. to about 200° C. In anotherembodiment, shells are grown at a temperature ranging from about 220° C.to about 250° C. In some embodiments, shells are grown at a temperatureranging from about 235° C. to about 245° C.

In some embodiments, shells can be deposited on monodisperse orsubstantially monodisperse InAs nanocrystals according to the methodsset forth in U.S. patent application Ser. No. 10/763,068, which ishereby incorporated by reference in its entirety.

The foregoing methods provide a “one-pot” synthesis of monodisperse orsubstantially monodisperse as-prepared InAs nanocrystals, including InAsnanocrystals demonstrating core/shell architectures.

In a further aspect, a method of determine the core size of nanocrystalshaving a core/shell architecture is provided. In one embodiment, amethod for determining the core size of a core/shell nanocrystalcomprises determining the size of the core/shell nanocrystal, the corecomprising a material M¹X¹ and the shell comprising a material M²X²,wherein M¹ and M² are cations and X¹ and X² are anions, determining theratio of M¹ to M², and correlating the ratio of M¹ to M² to the volumeof the core of the nanocrystal. In some embodiments, the ration of M¹ toM² can be correlated to the volume of the core by providing a sphericalmodel. A spherical model, according to some embodiments, assigns thecore of the core/shell nanocrystal a spherical shape.

In some embodiments, a material M¹X¹ and a material M²X² areindependently selected from a II/VI compound or a III/V compound. Insome embodiments, a material M¹X¹ comprises InAs.

Embodiments of the present invention are further illustrated in thefollowing non-limiting examples.

EXAMPLES Materials for Examples 1-5

1-octadecene (90%, Aldrich), Indium acetate (In(Ac)₃, 99.99%)Tri-n-octylphosphine (TOP, 97%), tris-(trimethylsilyl)phosphine((TMS)₃P, 98%), 1-octylamine (Alf 99%) stearic acid (SA, 98%), cadmiumstearate and selenium powder (Se, 9.999%) were purchased from Alfa. Zincoxide (ZnO, 99.99%) and octanoic Acid (98%) were purchased from Adrich.Indium stearate and tris-(trimethylsilyl)arsenide (As(TMS)₃) weresynthesized according to the literature procedure respectively. Zincprecursor and cadmium precursor were prepared by heating a mixture ofZnO and octanoic acid or CdO and octanoic acid at 250° C. respectively,then zinc and cadmium precursors were purified by the addition ofacetone, and the precipitation was dried under the vacuum respectively.

Stock Solutions

Cadium stock solution. A solution of 0.2 M Cd in ODE was prepared asfollowed: 2 mM cadmium precursor, 2 mM octylamine (0.7 ml) and ODE (9.3ml) were loaded into flask and heated to 80° C. under argon. When thesolution was clear, it was cooled to room temperature.Zinc stock solution. A solution of 0.2 M Zn in ODE was prepared asfollowed: 2 mM zinc precursor, 2 mM octylamine (0.7 ml) and ODE (9.3 ml)were loaded into flask and heated to 80° C. under the argon. When thesolution was clear, the solution was cooled to room temperature.Selenium stock solution. A solution of 0.2 M selenium was prepared bymixing 2 mM selenium (0.158 g) with TOP (10 ml) in a glovebox.

Example 1 As Prepared Monodisperse or Substantially Monodisperse InAsNanocrystals

0.4 mM indium stearate, 0.5 ml TOP and 3.5 ml ODE were loaded intothree-neck-flask. This mixture was heated to 150° C. under argon flow.An As(TMS)₃ solution made in glovebox was subsequently injected intoreaction mixture, and then the reaction mixture was heated up to 300° C.for the growth of monodisperse or substantially monodisperse InAsnanocrystals. To monitor the growth of the nanocrystals, aliquots weretaken at different reaction times for absorption and emissionmeasurement. FIG. 7 illustrates the as-prepared monodisperse orsubstantially monodisperse InAs nanocrystals of Example 1.

Example 2 As Prepared Monodisperse or Substantially MonodisperseInAs/InP Nanocrystals

InAs core nanocrystals synthesized in Example 1 were cooled to 110° C.0.3 mM stearic acid (0.5 ml in ODE) was injected into the reactionmixture. A mixture of 1 mM octylamine (0.2 ml) and 0.2 mM (TMS)₃P in ODE(0.8 ml) was subsequently added into reaction mixture dropwise. Afterthe addition of P precursor, the mixture was heated to 178° C. andmaintained 45 minutes for the growth of InP shell onto the InAs core.

Example 3 As Prepared Monodisperse or Substantially MonodisperseInAs/InP/ZnSe Core/Shell/Shell Nanocrystals

InAs core nanocrystals synthesized in Example 1 were cooled to 110° C.and 0.3 mM Stearic acid (0.5 ml in ODE) was injected into the reactionmixture. A mixture of 1 mM octylamine (0.2 ml) and 0.2 mM (TMS)₃P in ODE(0.8 ml) was subsequently added to the reaction mixture dropwise. Afterthe addition of P precursor, the mixture was heated to 178° C. andmaintained 45 minutes for the growth of InP shell onto the InAs core.

Next, the same procedure was adopted for the growth of the ZnSe shell.When the indium precursor was depleted in the reaction mixture, 0.04 mMSe in TOP (0.2 ml) was injected into reaction vessel with InAs/InPnanocrystals. After 5 minutes, the same amount of zinc precursor wasinjected into reaction mixture. The temperature was subsequentlyincreased to 220° C. for 30 mM to allow the growth of ZnSe shell. Tomonitor the growth of the nanocrystals, aliquots were taken at differentreaction times for absorption and emission measurement. When thesynthesis was complete, the reaction was cooled to room temperature.

Example 4 As Prepared Monodisperse or Substantially MonodisperseInAs/CdSe Core/Shell Nanocrystals

The solution of InAs nanocrystals prepared in Example 1 was set at 180°C. 0.04 mM Se in TOP (0.2 ml) was subsequently injected into reactionvessel containing the InAs nanocrystals. After 5 minutes, the sameamount of cadmium precursor was injected into reaction solution. Thetemperature of the reaction mixture was increased to 190° C. for 30 minto allow the growth of CdSe shell. To monitor the growth of thenanocrystals, aliquots were taken at different reaction times forabsorption and emission measurement. When the synthesis was complete,the reaction was cooled to room temperature.

Example 5 As Prepared Monodisperse or Substantially MonodisperseInAs/ZnSe Core/Shell Nanocrystals

The solution of InAs nanocrystals prepared in Example 1 was set at 180°C. 0.4 mM Se in TOP (0.2 ml) was injected into the reaction vesselcontaining the InAs nanocrystals. After a time period of 5 minutes, thesame amount of Zn precursor was injected into the reaction solution. Thetemperature of the reaction mixture was increased to 220° C. for 30minutes to allow the growth of the ZnSe shell. To monitor the growth ofthe nanocrystals, aliquots were taken at various reaction times forabsorption and emission measurement. When the synthesis was complete,the reaction mixture was cooled to room temperature.

It should be understood that the foregoing relates only to preferredembodiments of the present invention and that numerous modifications oralterations may be made therein without departing from the spirit andthe scope of the present invention as defined in the following claims.

1. As-prepared indium-arsenide (InAs) nanocrystals comprising aphotoluminescence emission line having a full-width at half maximum(FWHM) of about 55-85 nm.
 2. The InAs nanocrystals of claim 1, whereinthe photoluminescence emission line has a FWHM of about 55-65 nm.
 3. TheInAs nanocrystals of claim 1 having photoluminescence at a wavelengthranging from about 700 nm to about 1400 nm.
 4. The InAs nanocrystals ofclaim 1 having an average size less than about 5 nm.
 5. The InAsnanocrystals of claim 1 having an average size less than about 2 nm. 6.As-prepared core/shell nanocrystals comprising an InAs core and at leastone shell, the core/shell nanocrystals comprising a photoluminescenceemission line having a FWHM of about 55-85 nm.
 7. The core/shellnanocrystals of claim 6, wherein the photoluminescence emission line hasa FWHM of about 60-75 nm.
 8. The core/shell nanocrystals of claim 6having a photoluminescence wavelength ranging from about 700 nm to about1400 nm.
 9. The core/shell nanocrystals of claim 6, wherein the at leastone shell comprises a II/VI compound or a III/V compound.
 10. Thecore/shell nanocrystals of claim 6, wherein the core/shell nanocrystalshave a photoluminescent quantum yield (PL QY) up to about 90%.
 11. Thecore/shell nanocrystals of claim 6, wherein the core/shell nanocrystalshave a PL QY of at least 40%.
 12. The core/shell nanocrystals of claim6, wherein the core/shell nanocrystals have a PL QY of at least 30% inaqueous media.
 13. The core/shell nanocrystals of claim 6 having ahydrodynamic size of less than about 10 nm.
 14. The core/shellnanocrystals of claim 9, wherein the at least one shell comprises aplurality of monolayers of the II/VI compound or the III/V compound. 15.The core/shell nanocrystals of claim 6 further comprising at least oneligand associated with surfaces of the nanocrystals.
 16. The core/shellnanocrystals of claim 6 comprising a plurality of shells.
 17. A methodof synthesizing InAs nanocrystals comprising: a) combining an indium(In) precursor, a ligand, and a solvent to form an In-ligand complex; b)admixing an arsenic (As) precursor with the In-ligand complex at a firsttemperature sufficient to form InAs nanocrystals; and c) heating theInAs nanocrystals to a second temperature to provide substantiallymonodisperse InAs nanocrystals.
 18. The method of claim 17, wherein thesecond temperature is greater than the first temperature.
 19. The methodof claim 17, wherein the InAs nanocrystals have a first concentration atthe first temperature, and the substantially monodisperse InAsnanocrystals have a second concentration at the second temperaturewherein the second concentration is less than the first concentration.20. The method of claim 17, wherein the InAs nanocrystals have a firstaverage size at the first temperature, and the substantiallymonodisperse InAs nanocrystals have a second average size at the secondtemperature, wherein the first average size is less than the secondaverage size.
 21. The method claim 17, further comprising forming afirst shell comprising a material M¹X¹ on at least one of thesubstantially monodisperse InAs nanocrystals, wherein M¹ is a cation andX¹ is an anion.
 22. The method of claim 21, wherein forming the firstshell on at least one of the substantially monodisperse nanocrystalscomprises contacting the substantially monodisperse InAs nanocrystals,in an alternating manner, with a cation (M¹) precursor solution in anamount to form a monolayer of the cation, and an anion (X¹) precursorsolution in an amount to form a monolayer of the anion, wherein M¹X¹comprises a stable, nanometer sized inorganic solid and wherein M¹X¹ isselected from a TIN compound or a III/V compound.
 23. The method ofclaim 22 further comprising forming subsequent shells comprising amaterial M²X² by contacting the substantially monodisperse InAsnanocrystals having the first shell, in an alternating manner, with acation (M²) precursor solution in an amount to form a monolayer of thecation, and an anion (X²) precursor solution in an amount to form amonolayer of the anion, wherein M²X² comprises a stable, nanometer sizedinorganic solid and wherein M²X² is selected from a II/VI compound or aIII/V compound.
 24. A method of determining the core size of acore/shell nanocrystal comprising: determining the size of thecore/shell nanocrystal, the core comprising a material M¹X¹ and theshell comprising a material M²X², wherein M¹ and M² are cations and X¹and X² are anions; determining the ratio of M¹ to M²; and correlatingthe ratio of M¹ to M² to the volume of the core of the nanocrystal.